Ultra-hard boride-based metal matrix reinforcement

ABSTRACT

A composite of M/AlMgB 14  or M alloy/AlMgB 14  is synthesized, where M=Al, Ti, W, or Cu. Small particles and/or fibers of AlMgB 14  are distributed throughout a metal matrix to strengthen the resulting composite.

GRANT REFERENCE

This research was federally funded under DOE Contract No. DOE-EE ED 19/2803/AMES and DOE Contract No. W-7405-ENG-82. The government may have certain rights in this invention.

FIELD OF THE INVENTION

The field of the invention involves an ultra-hard boride-based reinforcement, AlMgB₁₄, for metals and metal alloys.

BACKGROUND OF THE INVENTION

This invention partially relates to an advancement on our prior patents, U.S. Pat. No. 6,099,605 and its division, U.S. Pat. No. 6,432,855; the first issued Aug. 8, 2000 and the second Aug. 13, 2002. Those patents relate to a ceramic material which is an orthorhombic boride of the general formula: AlMgB₁₄. Crystallographic studies indicate that the metal sites are not fully occupied in the lattice so that the true chemical formula may be closer to Al_(0.75)Mg_(0.78)B₁₄ which is contemplated by the formula here used as AlMgB₁₄. The ceramic is a superabrasive, and in most instances provides a hardness of 30 GPa or greater. This invention relates to an improvement involving the use of AlMgB₁₄ and related compositions as a strengthening reinforcement in metals, particularly Al and Al alloys.

Particulate and fiber reinforced metals have been known for decades and commercially available for at least a decade. The composites reinforce the metal matrix while still maintaining favorable metalworking characteristics and metal-like properties.

The primary objective of this improvement invention is to provide a new, strong metal composite, with the particular and preferred case of aluminum and its alloys here cited as a prime example. However, use of AlMgB₁₄ as a reinforcement is not limited to Al and Al alloys, but can be used with other metals (M). For example, the boride is also expected to provide a similar reinforcement effect in alloys of titanium, tungsten, and copper.

SUMMARY OF THE INVENTION

A composite of M/AlMgB₁₄ or M alloy/AlMgB₁₄ is synthesized, where M represents a metal such as Al, Ti, Cu, or W. Small particles or fibers of AlMgB₁₄ are distributed throughout the metal matrix to strengthen the resulting composite and may be used at levels up to 50% by volume.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a scanning electron microscope view of an Al/AlMgB₁₄ composite grown from the melt and provides an example of a particulate reinforcement.

FIG. 2 shows a typical fiber reinforcement morphology. Both manifestations of FIGS. 1 and 2 are possible depending on the cooling rate.

FIG. 3 is a stress-strain curve for Al and the Al/AlMgB₁₄ composite.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

Small particles or fibers of AlMgB₁₄ are distributed throughout metal or metal alloy matrix, such as Al, Ti, W, or Cu to strengthen the resulting composite and offer improved high-temperature stability relative to existing discontinuously-reinforced structures based on additions of SiC, Al₂O₃, BN, B₄C, TiC or TiB₂. The additives in discontinuously-reinforced metal matrix composites (MMC) are added at levels below the percolation threshold; that is, no network of additives is formed. If too much reinforcement is added to the metal matrix, the resulting composite material becomes brittle. Generally the amount should be from 5% to 30% on a volume basis.

As a majority of the prior art has focused on aluminum and aluminum alloys, the following discussion will employ this class or MMCs as the primary illustration of the concept. SiC reinforcement is reported to react with Al at elevated temperature, which degrades the matrix reinforcement interface. Wettability of SiC with Al is not good. Also, the 3.23 g/cc density is somewhat higher than ideal. BN reinforcements exhibit low strength and low ductility. The density of TiB₂ is 4.5 g/cc, which is twice that of aluminum, leading to segregation problems in the melt. B₄C (2.51 g/cc) has about the right density to match molten aluminum, but cannot be grown out of solution and is not amenable to solution processing. When B₄C is ground oxides form that subsequently degrade the Al-reinforcement interface. Al₂O₃ has a density of 3.97 g/cc which is too high to form a homogenous mixture with molten aluminum or molten aluminum alloy. TiC₂ has a density of 4.93 g/cc which is also too high to form a homogeneous mixture with molten aluminum or molten aluminum alloy. AlMgB₁₄ particulates and fibers possess improved wettability with Al, leading to better load transfer from the matrix, and improved high temperature stability.

At room temperature, the density of AlMgB₁₄ is 2.67 g/cc, nearly identical to that of Al (2.70 g/cc). At temperatures above the melting point of Al (660° C.), the densities differ by only 12% as the density of Al decreases to 2.35 g/cc. These nearly equal densities make segregation problems (i.e. floating or sinking particles and/or fibers) in the melt, inherent with other additives, of minimal concern for Al/AlMgB₁₄.

The rapid stirring of the melt necessary to avoid segregation in most MMCs can entrain nascent oxide films and gaseous species (particularly hydrogen) into the melt, degrading properties of the composite. However, with an Al/AlMgB₁₄ composite, only slow or minimal stirring is needed to maintain a uniform distribution of particles or fibers, which greatly reduces the problems with oxides and gas pick-up. Thus, the resulting distribution of AlMgB₁₄ reinforcement is highly uniform throughout the ingot. Moreover, AlMgB₁₄ reinforcement can be introduced in-situ by a solution-growth technique, in which the desired hard phase nucleates out of the Al melt. By proper control of the cooling rate to obtain a high nucleation rate combined with a slow growth rate, ultra-fine (nanophase) boride reinforcement particles or fibers form throughout the matrix, resulting in enhanced strengthening. Since the AlMgB₁₄ crystals nucleate directly from an aluminum flux, the surface energy between the particle and matrix should be low, resulting in highly efficient load transfer to the hard phase. An important part of this invention is the melt processing. There is no oxide interface between aluminum and AlMgB₁₄. Therefore, the strength of the interface is maximized. Any Al₂O₃ is taken off as slag.

Heat treatment studies indicate that the AlMgB₁₄ particles in an Al matrix are stable and do not react with the matrix, thereby preserving the integrity of the interface. The reinforced aluminum composite possessing the microstructure shown in FIG. 2 was heat treated in air at 400° C. (752° F.), a temperature equal to 72% of the absolute melting point of aluminum, for 96 hours. Following the heat treatment, the resulting microstructure was examined and found to be indistinguishable from that of the as-cast material, with no observable coarsening or redistribution of the boride reinforcement phase. As a result, an AlMgB₁₄ reinforced aluminum alloy may be used at higher temperatures than existing composites, which is of considerable interest to the aerospace community.

There are at least four methods of making Al/AlMgB₁₄ composites detailed in Examples 1-4. The following examples are offered to illustrate but not limit the invention.

EXAMPLE 1 Synthesis of Al/AlMgB₁₄ Composite In Situ

The following is a prophetic example. 1672.76 g (62 mol; 91.6 wt. %) Al is melted above the melting temperature of Al (660° C.). 129.72 g (12 mol; 7.1 wt. %) B and 24.31 g (I mol; 1.3 wt. %) Mg are added. Natural convection in the liquid disperses the B and Mg; typically 5 to 60 minutes is sufficient time for dispersion. The composite is cooled; crystals and fibers form of AlMgB₁₄ within the metal matrix. Part of the reason this example works is that the surface energy of AlMgB₁₄ is nearly the same as the surface energy of Al. This method is a preferred method to the extent that finer reinforcement particles and fibers are produced.

EXAMPLE 2 Synthesis of Al/AlMgB₁₄ Composite

The following is a prophetic example. 100 g Al is melted above 660° C. and below about 1500° C. Enough AlMgB₁₄ is added to comprise about 5 vol. % to about 30 vol. % of the total solution, and the liquid is slowly stirred to distribute the AlMgB₁₄ particles throughout the liquid metal. The AlMgB₁₄ is not melted (m.p. ≈2100° C.), nor is it formed in situ. Instead, AlMgB₁₄ is simply added to the Al solution and the solution is cooled.

EXAMPLE 3 Synthesis of Al/AlMgB₁₄ Composite by Cold Pressing

The following is a prophetic example. 100 cc Al powder is added to 5 cc to 30 cc AlMgB₁₄ powder. The density of AlMgB₁₄ is 2.67 g/cc. The particle size of the Al is from 10 nm to 100 μm. The particle size of the AlMgB₁₄ is from 10 nm to 100 μm. The smaller the particle, the stronger is the reinforcement. However, smaller particles aggregate. In any case, particles less than 10 μm are preferred. The powders are mixed and transferred into an appropriate mold. Hydraulic force is used to compress the particulates together. Alternatively, cold isostatic pressing may be used; high fluid pressure is applied to a powder part at ambient temperature to compact it into a predetermined shape. The pressure in a cold isostatic press chamber may reach 100,000 psi. Water or oil is usually used for the pressure medium. The product is a dense preformed metal composite which may be subsequently sintered to improve strength and reduce porosity.

EXAMPLE 4 Synthesis of Al/AlMgB₁₄ Composite by Hot Pressing

The following is a prophetic example. This example is the same as Example 3 except that a sample is heated when densified. Hot isostatic presses involve a heated argon atmosphere or other gas mixtures and pressures up to 100,000 psi. The product is a dense preformed metal composite. The disadvantage of hot pressing is that the metal, grains tend to grow during hot pressing. It is better to preserve small grain sizes.

EXAMPLE 5 Synthesis of Al/AlMGB₁₄ Composite in Situ

The following is a prophetic example. 1672.76 g* of standard Al alloy 5050 (Aluminum Association numbering system) (98.6 wt. % Al, 1.4 wt. % Mg) is melted above the melting temperature (˜650° C.). 127.89 g (12 mol; 7.1 wt. %) B are added. Natural convection in the liquid disperses the B; typically 5 to 60 minutes is sufficient time for dispersion. The composite is cooled; crystals and fibers form AlMgB₁₄ within the Al matrix. Part of the reason this example works is that the surface energy of AlMgB₁₄ is nearly the same as the surface energy of Al. This method is a preferred method to the extent that finer reinforcement particles and fibers are produced. It has an advantage over Example 1 in that volatile Mg metal is already present in this alloy and thus Mg need not be added.

From the above previous description and examples it can be seen that the invention, at least accomplishes the stated objectives. 

1. A reinforced alloy comprising metal or a metal alloy with up to about 50 vol. \fs\% of AlMgB₁₄ in the form of particles and/or fibers to reinforce said alloy.
 2. The reinforced alloy of claim 1 wherein the metal is Al or an Al alloy with from about 5 vol. % to about 30 vol. % of AlMgB₁₄ in the form of particles and/or fibers.
 3. The reinforced Al alloy of claim 2 wherein the Al alloy comprises from 90 wt. % to 100 wt. Al; from 0 wt. % to 7.0 wt. % Cu; from 0 wt. % to 1 wt. % Bi; from 0 wt. % to 1 wt. Pb; from 0 wt. % to 2 wt. % Fe; from 0 wt. % to 6 wt. % Mg; from 0 wt. % to 2 wt. Mn; from 0 wt. % to 14 wt. % Si; and from 0 wt. % to 8 wt. % Zn.
 4. The reinforced Al alloy of claim 2 wherein the Al alloy is from 80 wt. % Al to 100 wt. % Al; and the solid density of said reinforced alloy is from 2.50 g/cc to 2.90 g/cc.
 5. The reinforced Al alloy of claim 4 wherein the solid density of said reinforced alloy is from 2.60 g/cc to 2.80 g/cc.
 6. A method of making a reinforced Al or Al alloy comprising: providing Al; providing AlMgB₁₄ powder or grit; mixing the Al with the AlMgB₁₄; and cold pressing the Al with the AlMgB₁₄ until the composite holds together and the desired density of the composite is reached; and mechanically deforming or sintering at from 200° C. to 500° C.
 7. A method of making a reinforced Al or Al alloy comprising: providing Al powder; providing AlMgB₁₄ powder or grit; mixing the Al powder with the AlMgB₁₄; and hot pressing the Al with the AlMgB₁₄ between 200° C. and 550° C.
 8. A method of making a reinforced Al or Al alloy comprising: adding Al or Al alloy; adding B and Mg in quantities to be determined by the desired volume fraction of the reinforcement phase wherein the mole ratio of Mg to B is from about 1:10 to 1:14; melting the Al or Al alloy and dissolving the Mg and B in the Al or Al alloy; and cooling the mixture.
 9. The method of claim 8 wherein the mole ratio of Al to Mg to B is approximately 30:1:6 to 62:1:12.
 10. A method of making a reinforced Al or Al alloy comprising: melting the Al or Al alloy at a temperature from 660° C. to 1000° C.; adding AlMgB₁₄ to the melt of a particle size of 0.5 um to 100 um to the melt in a quantity of from 5% to 50 volume percent; and thereafter cooling the mixture. 